JP2006009232A - Method for producing antibacterial/antifungal/antiviral fiber - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an anti-microbial fiber to which the adsorption force of an anti-microbial agent is strong, which has a high anti-microbial property, also after washed, and is safer than other fibers, and from which the elusion of the anti-microbial property is extremely little. <P>SOLUTION: This method for producing the antibacterial/antifungal/antiviral fibers comprises attaching an aqueous suspension containing a pyridine-based anti-microbial agent having an inorganic value/organic value of 1.4 to 3.3 in a state dispersed in a fine particle state to synthetic fibers, pressing the fine particulate pyridine-based anti-microbial agent in spaces among the synthetic fibers and then subjecting the fibers to a thermal permeation treatment. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing antibacterial / antifungal / antiviral fibers.

  Conventionally, a fiber structure imparted with antibacterial properties has been widely used in various clothing, bedding, interior products, and the like. Particularly in recent years, hospital infection due to methicillin-resistant Staphylococcus aureus (hereinafter referred to as “MRSA”) has become a problem, and the use of antibacterial fibers that impart antibacterial properties to lab coats and curtains is increasing.

  In recent years, antibacterial efficacy under low humidity conditions by the bacterial transfer method has been introduced due to the problem of securing antibacterial efficacy in an evaluation method according to actual use scenes and ensuring safety considering the transfer of antibacterial agents from fibers to the skin. In the force test, there is a need for a fiber structure that has high antibacterial activity even after industrial washing and that has very little elution of the antibacterial agent from the fiber. Furthermore, in order to enhance hygiene, there is a need for fibers having not only antibacterial but also antifungal properties. In addition, virus problems such as SARS (Severe Acute Respiratory Syndrome) virus, avian influenza virus and human influenza virus are growing, and antiviral fibers are required.

  For example, an antibacterial fiber structure containing a pyridine antibacterial agent having a molecular weight of 200 to 700, an inorganic value / organic value = 0.3 to 1.4, and an average particle size of 2 μm or less is excellent in industrial washing durability. It is described in Patent Document 1 that it has antibacterial activity.

  Furthermore, Patent Document 2 and Patent Document 3 describe that a material obtained by treating pyrithione zinc with polyester fiber is a good antibacterial fiber even after washing.

JP 2000-8275 A JP-A-61-239082 JP 2000-1119960 A

  However, in each of the above-mentioned documents, those having the required antibacterial property, antifungal property, washing resistance and the like have not been obtained. That is, the method described in Patent Document 1 describes that when the inorganic value / organic value exceeds 1.4, the antibacterial agent is poorly adsorbed on synthetic fibers such as polyester and the antibacterial efficacy is also poor. Moreover, it cannot be said that the synthetic fiber to which the antibacterial agent is attached by the methods described in Patent Documents 2 and 3 has sufficient antibacterial activity and antifungal properties by the bacteria transfer method in a low humidity state. Further, fibers having an antiviral effect have not been known so far.

  Therefore, the present invention has strong antibacterial agent adsorptive power to fibers, high antibacterial properties even after washing, and very little antibacterial agent elution from synthetic fibers, thus providing safer antibacterial / antifungal / antiviral properties. The purpose is to provide fibers.

  In the present invention, an aqueous suspension in which a pyridine-based antibacterial agent having an inorganic value / organic value of more than 1.4 and less than 3.3 is dispersed in a fine particle state is attached to or attached to a synthetic fiber. Then, by applying mechanical pressure to push the particulate pyridine antibacterial agent into the gap between the synthetic fibers, and then heat osmosis treatment, the above problem by the method of manufacturing antibacterial / antifungal / antiviral fibers It was solved.

  When the inorganic value / organic value exceeds 1.4, since it has moderate hydrophilicity, a high antibacterial effect can be obtained even in a low humidity state. On the other hand, when the inorganic value / organic value is 3.3 or less, it has moderate hydrophobicity, so that elution from the fiber can be suppressed and antibacterial properties can be maintained even after washing.

Hereinafter, the present invention will be described in detail.
In this invention, an aqueous suspension in which a pyridine-based antibacterial agent having an inorganic value / organic value of more than 1.4 and less than or equal to 3.3 is dispersed in a fine particle state is attached to a synthetic fiber, and mechanical pressure is increased. The antibacterial / antifungal / antiviral fiber is produced by pressing the fine pyridine antibacterial agent into the gaps between the synthetic fibers and then heat osmosis.

  The above “inorganic values” and “organic values” are values that treat the polarity of various organic compounds invented by Mr. Minoru Fujita in an organic concept [reform chemical chemistry-organic chemistry-Kawai Shobo ( 1971)], and then systematically compiled by Yoshio Koda [Organic Conceptual Diagram-Fundamentals and Applications-Sankyo Publishing (1984)]. This “inorganic value” represents a characteristic as an ionic bond, and “organic value” represents a characteristic as a covalent bond. Generally, as the “inorganic value” increases, hydrophilicity, When the “organic value” is high, it tends to be hydrophobic. These values are determined as shown in Table 1.

  Furthermore, the inorganic value of the metal in the chelate compound, which is considered to have an intermediate property between ionic bond and covalent bond, varies depending on the coordination state. In general, heavy metals such as copper have strong covalent bonds [see Yoshio Koda, Organic Conceptual Diagram-Fundamentals and Applications-Sankyo Publishing (1984), page 128], chelate compounds containing copper The inorganic value is considered to be the lowest value 400 for heavy metals. However, since the case where the ion binding property is increasing is also considered, the value of 500 further exceeding this is also considered. However, in general, only inorganic values of inorganic substances take a specific value [see the organic conceptual diagram on page 22]. However, considering that heavy metals do not affect the organic-inorganic balance of the entire compound molecule, the inorganic nature of the metal It is considered that the value may be 0. In this case, the inorganic value of the metal in the chelate compound is a hypothetical minimum value of 0. Similarly, zinc is also a heavy metal, and values from 0 to 500 are conceivable. In the present invention, the “inorganic value / organic value” is a value obtained by calculating “the sum of the inorganic values” and “the sum of the organic values” of the values defined above, and taking the ratio of the two. Say.

  In general, when an antibacterial agent is adsorbed to a fiber, the closer the inorganic value / organic value between the antibacterial agent and the fiber, the better the affinity and the better the adsorbability. For example, the polyester fiber mentioned as the synthetic fiber is 0.7 and the nylon fiber is 1.7, and the antibacterial agents closer to this value tend to have better affinity for each fiber. Yes. However, when a pyridine antibacterial agent having an inorganic value / organic value of 3.3 or less is used, the polyester fiber can be converted into the synthetic fiber by the method according to the present invention in spite of the general tendency. It is possible to obtain fibers having good antibacterial, antifungal and antiviral properties.

  The inorganic value / organic value of the pyridine antibacterial agent used in the method according to the present invention needs to be more than 1.4 and 3.3 or less. To exceed 1.4 means to be 1.401 or more, for example. Furthermore, it is 1.46 or more, desirably 3.25 or less, desirably 1.8 or more, and more desirably 2.9 or less.

  When the inorganic value / organic value is 1.4 or less, for example, the polyester fiber having an inorganic value / organic value of 0.7 has a good affinity with the fiber and has a high hydrophobicity. Therefore, water elution is also suppressed, and it is generally considered advantageous. However, when the efficacy in the bacteria transfer method under low humidity conditions is examined, if the inorganic value / organic value is 1.4 or less, it becomes too hydrophobic, and the effectiveness drops extremely. Furthermore, since it is too oleophilic, it is easily affected by detergents, and washing resistance is deteriorated, which is not preferable. Therefore, the inorganic value / organic value needs to exceed 1.4. On the other hand, if the inorganic value / organic value exceeds 3.3, the hydrophilicity becomes too high, the adsorption to the fiber such as polyester is poor, the washing resistance is lowered because it is washed away with water, and the antibacterial from the fiber. Agent elution also increases, which is not preferable. Therefore, the inorganic value / organic value needs to be 3.3 or less.

  As a pyridine type antibacterial agent satisfying the above conditions, for example, 2-pyridinethiol copper-1-oxide (hereinafter referred to as “pyrition copper”) in which M in the following chemical formula (1) is Cu, and M is Zn. 2-pyridinethiol zinc-1-oxide (hereinafter referred to as “pyrithione zinc”) is exemplified, and zinc pyrithione is particularly desirable.

（式中ＭはＣｕ又はＺｎを示す。）

(In the formula, M represents Cu or Zn.)

  When the pyridine antibacterial agent is pyrithione zinc, the inorganic value is from Table 1, “bonds described in chemical formula (2) of pyrithione: 170 × 2 = 340”, “S bond: 20 × 2 = 40”. “Aromatic ring: 15 × 2 = 30”, and zinc can take a value of 0 to 500 as described above. Therefore, the sum of the inorganic values is in the range of 410-910. On the other hand, the organic value is “C: 20 × 10 = 200” and “S bond: 40 × 2 = 80”, which is 280 in total. Therefore, when this ratio is taken, the inorganic value / organic value = (410/280) to (910/280) = 1.46 to 3.25. If the inorganic value of zinc is the minimum value of 400 for heavy metals, the total inorganic value of pyrithione zinc is 810, and the inorganic value / organic value at that time is 2.9. These values are the same when the pyridine antibacterial agent is pyrithione copper.

  Therefore, the inorganic value / organic value of the pyridine antibacterial agent is 1.46 or more, preferably 3.25 or less, and more preferably 2.9 or less.

  The inorganic value / organic value of these pyridine antibacterial agents is slightly different from the inorganic value / organic value = 0.7 of the polyester fiber having high organic property. Nevertheless, when these pyridine antibacterial agents are treated on polyester fibers in water, the pyridine antibacterial agents are easily adsorbed on the polyester fibers. This is because the pyridine antibacterial agent dispersed in the state of fine particles having an inorganic value / organic value of 3.3 or less is more adsorbed on the surface of the polyester fiber than when it exists independently in water. This is considered to be stable.

  The water solubility of the above pyridine antibacterial agent is as low as 0.01 to 30 ppm. For example, the pyrithione zinc which is the above pyridine antibacterial agent has a water solubility at 25 ° C. of 8 ppm, and in the case of pyrithione copper, it is 1 ppm or less. These are preferably adsorbed on synthetic fibers having a high organic property, and are also preferably used with little elution into water or the like.

  Furthermore, the organic solvent solubility of the pyridine antibacterial agent is 0.01 to 100 ppm as solubility at 25 ° C. in n-octanol, which is an organic solvent generally used for n-octanol / water partition coefficient. Is difficult to dissolve and has low affinity. For this reason, the antibacterial agent is not easily micelle by the detergent at the time of washing, and the antibacterial activity can be maintained high even after washing.

  The pyridine antibacterial agent is attached to the synthetic fiber. In that case, it is necessary to make the pyridine antibacterial agent into the aqueous suspension.

  The aqueous suspension is obtained by stirring and / or pulverizing the pyridine antibacterial agent in the presence of a dispersant such as a surfactant and water, and the pyridine antibacterial agent is in a fine particle state. The suspension is dispersed in The average particle size of the pyridine antibacterial agent in this aqueous suspension is preferably 0.1 to 2 μm, and more preferably 0.1 to 1 μm. If the average particle size exceeds 2 μm, precipitation may occur, which may cause instability as a treatment agent. Also, the particle size is too large and adhesion to fibers during processing may be poor, or uneven adhesion may occur. There is a risk of it. Therefore, the pyridine antibacterial agent having a particle size of 2 μm or more is preferably 5% by weight or less, preferably 3% by weight or less, and preferably 1% by weight or less based on the total weight of the pyridine antibacterial agent. And more preferably 0.5% by weight or less.

  In addition, the average particle diameter of the particles of the pyridine antibacterial agent in the aqueous suspension is measured using a laser diffraction particle size distribution measuring device based on JIS R 1629, and the median diameter corresponding to a cumulative 50% is obtained. It is what I have sought.

  The dispersant is not particularly limited. For example, anionic surfactants such as lignin sulfonate, nonionic surfactants such as polyoxyethylene hydrogenated castor oil, and quaternary ammonium salt cationic surfactants. , PVA and the like. If necessary, a thickener, an antifreezing agent, and an antifoaming agent are added to these dispersants to form a slurry, and if necessary, a suspension is obtained using a ball mill, a ceramic mill or a pearl mill, and the above aqueous suspension is added. Use a suspension.

  The weight of the dispersant in the aqueous suspension is preferably 1/50 to 1/1 of the weight of the pyridine antibacterial agent, particularly preferably 1/25 to 1/2. When the amount of the dispersant is larger than this, the dispersant adheres to the fiber, the texture is impaired, and other dyeing auxiliary agents are adversely affected. On the other hand, if the amount is too small, the pyridine-based antibacterial agent settles and is not stable as a treating agent, and there is a possibility that a problem remains.

  The aqueous suspension is preferably an aqueous solution containing 50 to 99.99% by weight of water. When the water content is 50% by weight or more, precipitation and aggregation are unlikely to occur, the stability is excellent, and handling becomes easy.

  The pH of the aqueous suspension is preferably 4 to 9, and more preferably 5.5 to 8. This is because the pyridine antibacterial agent is decomposed in both cases where the pH is less than 4 or exceeds 9, and the antibacterial property is not maintained.

  The aqueous suspension is attached to the synthetic fiber. The method of attaching is not particularly limited, and a padding method in which the solution is immersed in the aqueous suspension in a bathtub and attached, a spray method in which the synthetic fiber is attached by spraying, or the like may be used.

  Moreover, when making the said aqueous suspension adhere to the said synthetic fiber, the density | concentration of the said pyridine type antibacterial agent has preferable 0.01-4 weight% with respect to water, More preferably, 0.1-1. 5% by weight. If it is 0.01% by weight or less, the amount of the pyridine antibacterial agent attached to the fiber is small, and sufficient antibacterial power is not exhibited. On the other hand, if it is 4% by weight or more, a large amount of the pyridine antibacterial agent will be consumed for its efficacy, which is not preferable.

  The aqueous suspension may be attached as it is or may be attached after diluting the aqueous suspension with water, but usually a thick suspension is prepared, It is preferable to dilute and use it at the time of use. For example, a 10 to 30% stock solution is prepared and diluted to a preferred concentration at the time of use. By doing so, the liquid can be stably stored for a long time, and the transportation cost to the site of use can be reduced.

  Furthermore, when making the said aqueous suspension adhere to the said synthetic fiber, you may add a dyeing agent and a dyeing auxiliary agent to the aqueous solution. For example, disperse dyes, acid dyes, cationic dyes, fluorescent whitening agents, water repellents, antifouling agents and the like generally used for fibers. Furthermore, if necessary, antibacterial agents such as zinc oxide and titanium oxide, insecticides, acaricides, flameproofing agents, antioxidants, fixing agents and the like may be added.

  Examples of the synthetic fibers to which the pyridine antibacterial agent is attached by the aqueous suspension include nylon fibers in addition to the polyester fibers and acrylic fibers. The polyester fibers include not only petroleum-derived fibers such as polyethylene terephthalate but also fibers obtained by modifying natural materials such as polylactic acid. Furthermore, natural fibers such as cotton, wool, and silk, and semi-synthetic fibers such as rayon fibers may be used in combination with the above synthetic fibers. Among these, polyester fibers are particularly desirable because they are excellent in industrial washing durability. The form of the synthetic fiber used in this way is not particularly limited, such as yarn, woven fabric, and non-woven fabric.

  The pyridine antibacterial agent is pushed into the gap between the synthetic fibers by applying mechanical pressure to the synthetic fibers to which the aqueous solution containing the aqueous suspension is adhered. The gap between the synthetic fibers indicates a gap between yarns and a gap between monofilaments constituting the yarn. In order to apply mechanical pressure, for example, the synthetic fiber to which the aqueous suspension is attached is passed between contacted rollers, or tension is applied between two non-adjacent rollers to which the synthetic fiber is applied. There is a method in which the pyridine antibacterial agent is pushed in between the fiber filaments by performing an operation such as applying pressure to the cloth or blowing air on a roller holding the fiber. In addition, the aqueous suspension is attached to a roller, and the synthetic fiber is sandwiched between the rollers so that the aqueous suspension is attached to the synthetic fiber, and at the same time, the pyridine-based antibacterial agent is added to the fiber of the synthetic fiber. There is also a method of pushing between the filaments.

  This pushing operation can push the pyridine antibacterial agent, which is in the form of fine particles in the aqueous suspension, into the fiber, and it is considered that strong adhesion that cannot be obtained simply by dipping can be obtained. And since the said pyridine type antibacterial agent adheres uniformly between fiber filaments, an effect is exhibited effectively by subsequent heat osmosis processing. At this time, the pushing operation can be performed satisfactorily by using the pyridine antibacterial agent as an aqueous suspension in which the pyridine antibacterial agent is present as fine particles instead of using the pyridine antibacterial agent as a complete solution. Further, when the particle diameter of the pyridine antibacterial agent satisfies the above conditions, it is desirable also in this pushing operation.

The contact portion of the roller that applies pressure to the synthetic fiber is preferably a flat metal and / or rubber. At this time, the desirable pressure applied to the synthetic fiber varies depending on the type and state of the fiber. This pressure is desirably 0.2 to 50 kg / cm ² . When the pressure is less than 0.2 kg / cm ^{2, the} pyridine antibacterial agent is not sufficiently pushed into the gap between the synthetic fibers, and when the pressure is 50 kg / cm ² or more, the burden on the synthetic fibers becomes too large. For example, in the case where 0.05 to 7 denier fibers are used, the amount of the aqueous suspension adhered to the fiber weight after the aqueous suspension contained in the fibers is squeezed by applying pressure. The pressure is preferably 5 to 100% owf, more preferably 30 to 80% owf, and 40 to 70% owf. Is more desirable. The pressure at which the aqueous suspension is less than 5% owf is not desirable because it needs to contain a certain amount of water in order to efficiently perform the subsequent heat osmosis treatment.

  The synthetic fiber that has been pushed in is subjected to a heat osmosis treatment to fix the pyridine antibacterial agent in the synthetic fiber.

  The appropriate temperature at which the heat osmosis treatment is performed is a temperature range that is equal to or higher than the Tg temperature (glass transition temperature) of the synthetic resin that constitutes the synthetic fiber, and that the synthetic fiber itself does not cause undesirable alteration such as decomposition. It is necessary to be. In addition, Tg temperature here is the value measured by the method described in JISK7121.

  In general, synthetic fibers made of a polymer are composed of regular and dense parts (crystal parts) and irregular and sparse parts (non-crystal parts), and the amorphous part is raised above the Tg temperature. Molecular chains are loosened, fluidity increases, and softening makes it easy for molecules such as antibacterial agents to enter. Therefore, when the pyridine antibacterial agent and the synthetic fiber are heat-treated at an appropriate temperature equal to or higher than the Tg temperature, the pyridine antibacterial agent efficiently penetrates into the fiber and is in a good fixing state. In particular, in the present invention, the pyridine antibacterial agent is strongly pressed between the fiber filaments by the above-mentioned indentation, so that it can efficiently penetrate into the non-crystalline part of the synthetic fiber by treating at the above-mentioned appropriate temperature, It adheres well.

  When the synthetic fiber is a polyester fiber, heat osmosis treatment at an appropriate temperature of (Tg + 80) to (Tg + 120) ° C. is desirable because the pyridine antibacterial agent can be most efficiently penetrated into the synthetic fiber. Specifically, since Tg of many polyester fibers is 70 to 80 ° C., the appropriate temperature is preferably 150 to 200 ° C., and preferably 160 to 190 ° C. The time for performing the heat osmosis treatment is appropriately selected and determined from the range of 20 seconds to 10 minutes. Preferably, it is 30 seconds to 5 minutes.

  When the synthetic fiber is a nylon fiber, heat treatment at (Tg + 40) to (Tg + 100) ° C. as the appropriate temperature is desirable because the pyridine antibacterial agent can be most efficiently permeated into the synthetic fiber. Since Tg ° C of general nylon fibers is 40 to 50 ° C, the appropriate temperature is preferably 80 to 150 ° C, and preferably 100 to 130 ° C. The time for performing the heat osmosis treatment is appropriately selected and determined from the range of 20 seconds to 3 minutes. Preferably, it is 30 seconds to 3 minutes. Moreover, when the said synthetic fiber is an acrylic fiber, Tg- (Tg + 60) degreeC is preferable and since TgdegreeC of an acrylic fiber is 80-90 degreeC, suitable temperature is 80-150 degreeC.

  Examples of the heat osmosis treatment method include a method of passing through a dryer, a method of passing a hot roller, a high-temperature steam heat treatment method (pad / steam method), and the like, and are not particularly limited.

  Moisture is required for fixing the pyridine antibacterial agent to the synthetic fiber by the heat osmosis treatment, and when the heat osmosis treatment is performed, the synthetic fiber contains at least 5% owf of water. preferable. This is presumably because the pyridine antibacterial agent requires some form of moisture when it penetrates into the softened part of the synthetic fiber. When the moisture adhering to the fiber is less than 5% owf, the moisture is too little, and the pyridine antibacterial agent is difficult to penetrate into the soft non-crystalline part of the synthetic fiber. There is a possibility that the washing resistance of the antiviral fiber is lowered.

  On the other hand, when performing the said heat osmosis process, it is desirable that the water | moisture content which the said synthetic fiber contains is 100% owf or less. If the water content exceeds 100% owf, the heat capacity of water is large, so that even if heated, the temperature of the synthetic fiber does not rise in a short time, and the non-crystalline part of the fiber does not become sufficiently soft, so that it penetrates. The above-mentioned pyridine antibacterial agent that cannot be dried is dried on the surface of the fiber, and the washing resistance of the finally obtained antibacterial / antifungal / antiviral fiber may be lowered. Moreover, the time and cost for finally drying those water | moisture contents will also be excessive.

  In the case where the synthetic fiber is a polyester-based fiber, the synthetic fiber that has been pushed in is subjected to a pre-drying treatment before the heat osmosis treatment, so that the heat osmosis treatment can be performed as described above. The moisture contained in the synthetic fiber may be reduced in advance. However, in that case, it is desirable that it is not less than 5% owf. The method for the preliminary drying treatment is the same as that used for the heat osmosis treatment, but the processing temperature is preferably 100 to 140 ° C.

  In addition, after the said heat osmosis process, in order to remove the excess processing agent and impurity which remain | survived on the said synthetic fiber, you may wash | clean and dry with water or an alkaline liquid. Also in this case, since the pyridine antibacterial agent is fixed in the synthetic fiber, the antibacterial property is not affected even if it is washed.

  The attached weight of the aqueous suspension by the pushing operation is preferably 5% by weight or more, and preferably 20% by weight or more with respect to the fiber weight. If the amount is less than 5% by weight, the fiber is too pressured and tends to damage the fiber. On the other hand, the upper limit of the adhesion weight is preferably 100% by weight. When the amount is more than 100% by weight, the pressure becomes low, and thus there is a tendency that the antibacterial agent is not sufficiently pushed into the fiber.

  The synthetic fiber to which the antibacterial agent is attached by the production method according to the present invention has an inorganic value / organic value of 3.3 or less of the antibacterial agent, a low water solubility of 30 ppm or less, and indentation and heat osmosis treatment. Because the antibacterial agent is firmly fixed by the water, the above pyridine antibacterial agent is hardly eluted even after water treatment such as washing, the antibacterial activity is kept high, and it is safe and excellent antibacterial / antifungal / antiviral It becomes the nature fiber. Furthermore, since the inorganic value / organic value of the antibacterial agent is moderately hydrophilic exceeding 1.4, the antibacterial agent is effective even under low humidity conditions such as experimental conditions in the bacterial transfer method, and antibacterial Antibacterial / antifungal / antiviral fiber with high efficacy.

  Furthermore, it is also effective for DNA viruses such as SARS virus, Lassa fever virus, Ebola hemorrhagic fever virus, AIDS virus, West Nile virus, Dengue virus, Japanese encephalitis virus, avian / human influenza virus, smallpox virus, herpes virus, etc. Antibacterial, antifungal and antiviral fibers with antiviral properties. In addition, it is considered that the antiviral effect is exerted on the fiber obtained by the production method according to the present invention due to the denaturing action of the antibacterial agent on the viral coat protein, and obtained by this production method. Antibacterial, antifungal, and antiviral fibers have antibacterial agents efficiently adhered to the fibers even after washing.

  Hereinafter, the present invention will be described more specifically with reference to examples. In the following text, “%” means “% by weight”. First, each test method and washing method will be described.

(Method for measuring the amount adsorbed on fibers)
The amount of adsorption was measured by measuring the amount of metal derived from the pyridine antibacterial agent contained in the fiber. That is, the fiber infiltrated with the pyridine-based antibacterial agent was ashed and treated with hydrochloric acid, and then the amount of metal in the residue was measured using an atomic absorption photometer, and then the amount of penetration of the pyridine-based antibacterial agent was calculated backward.

(Test bacteria and evaluation methods for antibacterial tests)
Antibacterial properties were evaluated using two types of Staphylococcus aureus (Staphylococcus aureus and MRSA) and Klebsiella pneumocniae. As evaluation objects, processed fabrics before and after washing were used.

  First, as a first evaluation method, a fungus transcription method (denoted as “bacteria transcription” in the table) described in an antibacterial test method for textiles defined in JIS L 1902 (2002) was performed. Judgment is made by comparing the decrease in the number of bacteria after 4 hours of culturing under low humidity by the number of bacteria recovered from each test cloth. The case where it was made effective ((circle)) and the case where it is less than 0.5 was made invalid (x).

  Further, as a second evaluation method, a bacterial liquid absorption method (indicated as “bacterial liquid” in the table) defined in JIS L 1902 (2002) was carried out. The determination was made effective (◯) when the bacteriostatic activity value of each test cloth was 2.2 or more, and invalid (x) when less than 2.2.

(Test fungus test method and evaluation method)
The antifungal property was evaluated using four types of fungi (Aspergillus niger, Penicillium citrinum, Chaetmium globosum, and Myrothecium verrucaria). As an evaluation method, the processed fabric before and after washing was used as in the antibacterial test. As an evaluation method, a wet method defined in JIS Z 2911 (2000) was performed. Judgment is effective (○) when the display method 0 of the antifungal test results (no growth of the hyphae is not observed in the inoculated part of the sample or test piece), and 1 (the hyphae recognized in the inoculated part of the sample or test piece) The area of the growth part is not more than 1/3 of the total area) and 2 (the area of the growth part of the mycelium found in the inoculated part of the sample or test piece is more than 1/3 of the total area) is invalid (X).

(Antiviral test and evaluation method)
The Center for Disease Control and Control of the People's Republic of China. Inactivation of SARS virus outside the body of the processed fabric after 50 times of industrial washing using a viral CPE (cytopathogenic effect) method in a culture system of African green monkey kidney passage cells (VERO E6: provided by Virus Test Center) The effect was evaluated by comparing with the virus control group.

Specifically, it is as follows.
<Process cloth and virus pretreatment>
Two strains of SARS virus (SARS-COV-P5: Coronavirus isolate, provided by the Virus Resource Center (Certificates of the People's Republic of China) Diluted with pure water so that the virus dilution concentration is 100 TCID50 (TCID50 = half the tissue culture infectious dose) provided by the Virus Resource Center (certified by the People's Republic of China Pharmaceuticals and Biological Products Examination Certificate: SH200400017). Was poured into a processed cloth after 50 times of industrial washing to fully infiltrate the cloth. This was left at room temperature for 10, 15, 30, 45 minutes, 1, 2, 3 hours, and then the virus diluted solution in the processed cloth was pushed out with aseptic tweezers to obtain a solution (hereinafter referred to as “treatment solution”). Obtained).

<Confirmation of inactivation effect by viral CPE method in VERO E6 cell culture system>
VERO E6 cells were inoculated at a concentration of 400,000 cells / ml into 96-well culture plates (provided by Beijing Takashiba Forest Biotechnology Co., Ltd.) and cultured at 37 ° C. for 24-48 hours to monolayer the cells. To this, 100 μl of each of the above-mentioned treatment liquids in each time course was put in 4 holes. This was cultured in an environment of 5% CO ₂ for 6 days, and the virus CPE was observed with an inverted microscope, and the result was recorded.

  The criteria at that time are as follows. “-” Indicates no change in viral cell CPE and 100% virus was inactivated, “+” indicates 25% or less CPE change and 75% virus inactivated, “++” indicates 26 50% inactivation with ~ 50% CPE change, "++++" not inactivated with 51-75% CPE change, 25% inactivation, "++++" not inactivated with 76-100% CPE change It shows that.

(Dissolution test method)
Measure the amount of pyridine antibacterial agent eluted from the processed fabric before washing into water ((1) in the table), 20% ethanol aqueous solution ((2) in the table), and 4% acetic acid ((3) in the table). did. Specifically, 20 g of the solution was immersed in 1 g of fiber in 20 ml of a solution at 40 ° C. for 10 days, the impure organic matter in the eluate was decomposed by hydrochloric acid treatment, and the remaining metal was measured with an atomic absorption photometer. The determination was good (◯) when the eluted pyridine antibacterial agent was less than 1% with respect to the total amount of pyridine antibacterial agent in the fiber, and poor (x) when it eluted 1% or more. The initial amount of the pyridine antibacterial agent in the fiber was measured by the method for measuring the amount of adsorption onto the fiber described above.

(Washing method)
Industrial washing was carried out by a washing method compliant with Ordinance No. 13 of the Ministry of Health and Welfare using a JAFET standard combination detergent specified by the Japan Textile Evaluation Technology Council (JTETC). Specifically, it was carried out 50 times under the condition of 80 ° C. (industrial washing). Home washing was performed by a washing method based on 103 of JIS L 0217. Specifically, washing was performed 10 times under normal temperature conditions.

(Production of aqueous suspension)
Next, the manufacturing method of aquatic suspension is demonstrated.
As a pyridine-based antibacterial agent, pyrithione zinc (manufactured by Arch Chemical Co., Ltd., abbreviated as “ZPT” in the table, where the inorganic value / organic value is calculated as 2.9 when the inorganic value of zinc and copper is 400). ) And pyrithione copper (manufactured by Arch Chemical Co., Ltd., abbreviated as “CuPT” in the table), and sodium pyrithione (calculated that the inorganic value / organic value is 5.0 when the inorganic value of sodium is 500) Manufactured by Arch Chemical Co., Ltd., abbreviated as “NaPT” in the table). Each physical property is as follows.
(Physical properties of zinc pyrithione)
Inorganic value / organic value: 2.9
・ Water solubility: 8ppm (25 ℃)
Organic solvent solubility (octanol): 5ppm
・ Average particle size: 0.5μm
-Ratio of particles of 2 μm or more: 0%
・ PH: 6.6
(Pyrithione copper properties)
Inorganic value / organic value: 2.9
・ Water solubility: 0.5ppm (25 ℃)
Organic solvent solubility (octanol): 0.3 ppm
・ Average particle size: 0.5μm
-Ratio of particles of 2 μm or more: 0.5%
-PH: 7.1
(Physiology of pyrithione sodium)
Inorganic value / organic value: 5.0 (value calculation is described in Table 2. In the table, “I / O value” is abbreviated.)
Water solubility: 53% (25 ° C)
Organic solvent solubility (octanol): 0.1 ppm
・ Average particle size: Water-soluble (complete dissolution)
-Ratio of particles of 2 μm or more: Water-soluble (complete dissolution)
-PH: 8.3

The above pyridine antibacterial agents were mixed in the following component ratios.
-Pyrithione zinc, pyrithione copper or pyrithione sodium: 20 parts by weight-Polyoxyethylene alkyl ether sulfate ester salt (dispersing agent, manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: Hightenol 08E): 3 parts by weight-Glycerin (freezing agent Wako Jun) Yaku Kogyo Co., Ltd.): 2 parts by weight and purified water: 75 parts by weight was mixed into a paste, and then pyrithione zinc and pyrithione copper were made into a suspension with an average particle size of 0.5 μm using a ceramic mill. Sodium pyrithione was stirred to form a transparent uniform liquid. The obtained aqueous fine particle suspension or transparent liquid was diluted with water so that the respective pyridine antibacterial agents would be 0.8% to obtain an aqueous suspension (aqueous transparent liquid for sodium pyrithione). The pH of the obtained aqueous suspension is 6.8 using pyrithione zinc, 7.1 using pyrithione copper, and 7.4 using sodium pyrithione, respectively.

(Synthetic fibers)
Synthetic fibers include polyester fibers (Fiber Tropical for Color Dyeing Company: 150 denier x 48 filaments manufactured by Toray Industries, Inc., abbreviated as “PET” in the table) and nylon fibers (Fiber Nylon Taffeta for Color Dyeing Company Testing: 70 denier × 24 filaments (abbreviated as “Nylon” in the table).

Example 1
The aqueous suspension of pyrithione zinc was placed in a bath, and 10 g of polyester fiber was immersed therein. Next, the polyester fiber was passed through a roller which was pressurized to 60% owf. After that, heat osmosis treatment is performed at 190 ° C. for 2 minutes with an atmospheric pressure dryer, and finally washed with water at room temperature for 5 minutes and then dried at 120 ° C. for 2 minutes to provide antibacterial / antifungal / antiviral fibers. A processed cloth was obtained. Table 3 shows the adsorptivity, elution, and antibacterial / antifungal evaluation results before and after industrial washing for this processed fabric. In the table, the inorganic value / organic value is expressed as “I / O value”.

(Example 2)
A processed cloth which is an antibacterial / antifungal / antiviral fiber was obtained in the same manner except that pyrithione copper was used in place of the pyrithione zinc of Example 1. Table 3 shows the evaluation results of this work cloth.

(Comparative Example 1)
A processed fabric was obtained in the same manner except that sodium pyrithione was used in place of pyrithione zinc in Example 1. Table 3 shows the evaluation results of this work cloth.

Example 3
The aqueous suspension of pyrithione zinc was placed in a bath, and 10 g of nylon fiber was immersed therein. The nylon fiber was then passed through a roller that was pressurized to 60% owf. After that, heat osmosis treatment is performed at 120 ° C. for 1 minute in an atmospheric pressure dryer, and finally washed with water at room temperature for 5 minutes, followed by drying at 110 ° C. for 2 minutes to provide antibacterial / antifungal / antiviral fibers. A processed cloth was obtained. Table 4 shows the results of the elution of the processed cloth and the antibacterial activity before and after home washing.

Example 4
A processed cloth which is an antibacterial / antifungal / antiviral fiber was obtained in the same manner except that pyrithione copper was used in place of pyrithione zinc in Example 3. Table 4 shows the evaluation results of this work cloth.

(Comparative Example 2)
A processed fabric was obtained in the same manner except that sodium pyrithione was used in place of pyrithione zinc in Example 3. Table 4 shows the evaluation results of this work cloth.

(result)
Antibacterial / antifungal / antiviral fibers manufactured using a pyridine antibacterial agent having an inorganic value / organic value exceeding 1.4 and not more than 3.3 have an inorganic value / organic value of 3. The antibacterial effect was more stable than that using more than 3 pyridine antibacterial agents, and no elution occurred.

(Example 5)
An antibacterial / antifungal / antiviral solution was prepared in the same manner as in Example 1, except that a diluted solution in which the concentration of pyrithione zinc in the aqueous suspension was changed from 0.8% to 0.67% was used. A processed cloth, which is a natural fiber, was obtained. The expected adsorption concentration at that time was 0.4%, and the actually measured concentration was 0.38%. Moreover, industrial washing was similarly performed 50 times at 80 degreeC. An antiviral test was performed using this processed cloth. The results are shown in Table 5. An inactivation effect on the virus appeared in 1 hour or more, and a 100% inactivation effect was obtained in 3 hours.
(Comparative Example 3: Control)
An antiviral test was performed using the above virus diluted solution that had not been treated with a processed cloth. The results are shown in Table 5.

Claims (7)

  After attaching or adhering an aqueous suspension in which a pyridine-based antibacterial agent having an inorganic value / organic value of more than 1.4 and less than 3.3 is dispersed in a fine particle state to a synthetic fiber, A method for producing antibacterial / antifungal / antiviral fibers, wherein mechanical pressure is applied to push the particulate pyridine-based antibacterial agent into the gap between the synthetic fibers, followed by heat osmosis treatment.   The method for producing antibacterial / antifungal / antiviral fibers according to claim 1, wherein when the heat osmosis treatment is performed, the moisture contained in the synthetic fiber is 5 to 100% by weight with respect to the fiber weight. The pyridine antibacterial agent is 2-pyridinethiol zinc-1-oxide and / or 2-pyridinethiol copper-1-oxide represented by the following chemical formula (1). A method for producing antibacterial, antifungal and antiviral fibers.

(In the formula, M represents Zn or Cu.)   The method for producing antibacterial / antifungal / antiviral fibers according to any one of claims 1 to 3, wherein an adhesion weight of the aqueous suspension is set to 5 to 100% with respect to a fiber weight by the pushing operation.   The method for producing antibacterial / antifungal / antiviral fibers according to claim 1, wherein the synthetic fiber is a polyester fiber, and the heat osmosis treatment is performed at 150 to 200 ° C. 5.   The method for producing antibacterial / antifungal / antiviral fibers according to claim 1, wherein the synthetic fibers are nylon fibers or acrylic fibers, and the heat osmosis treatment is performed at 80 to 150 ° C. 5.   The aqueous suspension contains a dispersant having a weight of 1/50 to 1/1 with respect to the pyridine-based antibacterial agent, and moisture is 50 to 50% of the total weight of the aqueous suspension. The method for producing antibacterial / antifungal / antiviral fibers according to any one of claims 1 to 6, which is a solution containing 99.99% by weight.